1, 1, 1-trichloro-2, 2-bis[(carboalkoxy-amino) aryl] ethane



United? rates .Patent a rtime ats aazfi Patented Oct. 16, 1962 3,959,021 1,1,1-TRIHLOR-2,2-BIS[{CARBOALKOXY- AMINQARYHEIHANE Erhard I. Prill, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Feb. 12, 1960, Ser. No. 8,246 4 Ciaims. (Cl. 260-471) The present invention relates to organic nitrogen compounds and more particularly provides a new and valuable series of chlorinated nitrogenous esters and the method of preparing the same.

According to the invention, there are provided certain l,1,l-trichloro2,2-bis(carboalkoxyaminoaryl)ethanes by the reaction of chloral with an alkyl ester of an N-aryl carbamic acid, substantially according to the scheme:

OlC CHO+2ArNHCOOAlk Cl CCH (ArNHCOOAlk) +H O wherein Ar denotes an aromatic hydrocarbon radical of from 6 to 12 carbon atoms which is attached to the remainder of the molecule of which it forms a part through a ring carbon atom thereof, and Alk denotes an alkyl radical of from 1 to carbon atoms.

Presently useful alkyl esters include those of carbanilic acid, i.e., compounds of the formula NHCOOAlk in which Alk is as above defined, R is selected from the class consisting of hydrogen and alkyl radicals of from 1 to 6 carbon atoms, n is an integer of from 1 to 4, and the total number of carbon atoms in the total number of R radicals is from 1 to 6. Examples thereof are the ethyl, methyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-amyl and tert-amyl carbanilates. Derivatives of said alkyl carbanilates wherein there is present one or more lower alkyl substituents are likewise useful. Thus, there may be employed the methyl, ethyl, propyl, butyl or amyl esters of such ar-alkylcarbanilic acids as the 2-, 3-, or 4-methylcarbanilic acid, 2-, 3-, or 4-ethylcarbanilic acid, 2-, 3-, or 4-n-propylcarbanilic acid, 2-, 3-, or 4- tert-butylcarbanilic acid, 2-, 3-, or 4-isoamylcarbanilic acid, or 2-, 3- or 4-hexylcarbanilic acid. Also useful are the alkyl esters of dior poly-alkylated carbanilic acids such as 3,4- or 2,3-dipropy-l carbanilic acid, the 2,3,5-trimethylcarbanilic acid, or tetramethy-lcarbanilic acid. Likewise useful are the alkyl phenylcarbanilates, i.e., the alkyl N-xenylcarbamates of the structure NHGOOAlk wherein Alk is as herein defined, and the alkyl N-naphthylcarbamates of the structure NH0 0 OAlk invention wherein chloral is reacted with the appropriate N-aryl carbamate:

1,1,1-trichloro-2,2-bis[4-(carbomethoxyamino)phenyl]- ethane l, l l-trichloro-2,2-bis [2- (carboethoxyamino)phenyl] ethane 1,1, l-trichloro-2,2-bis [2- (carb ois opropoxyamino) phenyl] ethane 1,1,1-trichloro-2,2-bis [4- (carbo-n butoxyamino phenyl] etha ne 1,1, l-trich1oro-2,2-bis [4-ethyl-2-(carbomethoxyamino)- phenyl] ethane 1,1, l-trichloro-2,2-bis [4-(carbomethoxyamino)- 2,3-dimethylphenyl] ethane 1, 1,1-trichloro-2,2-bis[2-n-propyl-4-(carbomethoxyamino) phenyl] ethane 1,1, l-trichloro-2,2-bis [4-phenyl-2-( carb obutoxyamino) phenyl] ethane 1, 1, 1 -trichloro-2,2-bis [2,3,5 -trimethyl-4-( carboamyloxyamino) -phenyl] ethane 1, 1, 1-trichloro-2,2-b is [2-amyl-3-butyl-4- (carboethoxyamino )phenyl] ethane 1,1,1-trichloro-2,2-bis[diisopropyl(carboethoxyamino)- phenyl] ethane l,1,1-trichloro-2,2-bis [2,3,4,5-tetramethyl-6- (carbometh oxyamino phenyl] ethane l,1,1-trichloro-2,2-bis[2-(carboethoxyamino)-1-naphthyl] ethane 1, 1, 1-trichloro-2,2-bis [.1 carb oprop oxyamino) -7-ethyl- I 2-naphthyl] ethane Reaction of the chloral with the arylcarbamate occurs at the aromatic nucleus. Thus with a methyl ethylcarbam'late the reaction proceeds as follows:

C0 3 HaCOOCHN- HzCH Condensation of the chloral with the carbamate occurs by simply mixing the two reactants, advantageously in the presence of catalyst or condensing agent, and allowing the mixture to stand until formation of the 1,1,1- trichloro-2,2-bis(carboalkoxyaminobenzenoid)ethane has occurred. Since the reaction is exothermic, generally no external heating is required. However, when working with large quantities, external cooling may be needed. Depending upon the nature of the individual N-aryl carbamate, a solvent or diluent may or may not be employed. Useful solvents are, e.g., aliphatic or aromatic hydrocarbons such as hexane, benzene or xylene; chlorinated hydrocarbons such as carbon tetrachloride or dichlorobenzene; ether such as ethyl ether or dioxane, etc. Since the reaction takes place by condensation of one mole of the chloral with two moles of the N-benzenoid carbamate, these reactants are advantageously employed in such stoichiometric proportions; however, an excess of either reactant may be employed since any unreacted reagent is readily recovered from the final reaction product.

While the condensation takes place in the presence or absence of a catalyst, it is generally advantageous to employ an organic or inorganic acidic material as catalyst. Examples of presently useful catalysts are sulfuric acid,

.4- toluenesulfonic acid, glacial acetic acid, acidic salts such as ferric chloride or boron trichloride, etc. Compounds of the Lewis acid type are generally useful. Although the reaction takes place readily at atmospheric pressure, it may be eflected at either super-atmospheric or sub-atmospheric pressures. Thorough stirring of the reaction mixture is recommended for dissipation .of the heat evolved in the exothermic reaction.

The presently provided l,1,l-trichloro- 2,2-bis[(carboalkoxyamino) aryllethanes are generally stable, highmelting solids or high-boiling viscous liquids which are advantageously employed for a variety of'commercial and biological purposes, e.g., as lubricant additives, plasticizers for synthetic resins and plastics, rubber-compounding constituents, etc. When used as plasticizers, they also impart flame-proofing efiect. The presently provided compounds are likewise useful as insecticides, fungicides and basteriostats.

The invention is further illustrated, but not limited, by the following examples: i

Example 1 Malian m th l sa ban e (1 1 a. 1 m e) was added to'concentrated' sulfuric acid (300 ml.) at 5,- C. with stirring; Chloral (73.5 g., 0.54 mole) was added in 5 minutes. No heat effect was noticeable. Stirring was continued without cooling and a slow reaction took the pot temperature from 12 C." to 43 C. in one hour. After an additional two hours the temperature had dropped to C. The contents of the flaskwas poured over ice. The white solid which precipitated was removedby filtration and was washed Well with water including one re-slnrry. product, 174g. (87% yield), melted at l9.6-8 C. with decomposition Two recrystallizations from acetone methanol gave white crystals of the substantially pure 1,1, l trichloro 2,2 bis[(4 carbomethoxyamino)phenyl]- ethane, melting at 207-9 C.,' and analyzing as follows:

The l,l,l-trichloro- 2,2-bis[(4-carbomethoxyamino) phenyl] ethane was converted to the prior art 1,1-dichloro-2,2-

bis (4-carbomethoxyamino) phenyl] ethylene, MP. 212.5-

. separation of solids.

After airdrying for two days the 214' C., by refluxing with potassium hydroxide in metha- I101. The structure of thepresently provided 1,1,1-trichloro 2,2-bis(4-carbometh0xyaminophenyl)ethane was thereby substantiated. 7

Operating as above, other alkyl carbanilates having from 1 to 5 carbon atom in the alkyl radical are similarly converted "to 'l,l,l-trichloro-2,2 bis[(carboalkoxyamino)phenyl]ethanes; thus, instead of the methyl carbanilate used above, there may be employed either ethyl, bntyljor amyl carbanilate or alkyl carbanilat'es carrying on the benzene ring thereof one" or more lower alkyl sub st itu'eu ts, e.gl, methyl 4-ethyl carbanilate or amyl 2,3-dimethyl carbanilate, Thus, reaction of chloral with amyl Z heityIcarbaniIateusing the procedure described above v s oxy) phenyl1ethane.

Exantple 2 mixture rose spontaneously to 37 C. The mixture was then warmed at 43 -"45 C. for 3 hours. The resulting dark green reaction mixture was then allowed to stand overnight at room temperature. At the end of that time it had turned to a clear, dark brown solution. It was poured on ice, with .stirring, and allowed to stand for After decanting the resulting aqueous layer, the solids were stirred in the Waring Blendor, and the milky upper layer was discarded. The'residual solids were rew ashed, first with water, then with arnrn0niacal water and finally with water. Upon oven-drying of the washed material there was obtained the powderlike 1,l,1,-trichloro 2,2 bis [1 car boethoxyamino) -2-naphthyllethane, analyzing 5.02% nitrogen as against 5.0%, the calculated value for C H H O Cl It was partly soluble in toluene, ethanol or ether and completely'solw ble in acetone.

The 1,1,1 trichloro-2,2-bis[(carboalkoxyaminohrylj ethanes posses bacteriostat effect at very low concentra-- tions. Thus, in vitro tests of the 1,1,l-triehloro-2,2.-bis l(4-carbomethoxyamino)phenyl] ethane of Example 1 showed inhibition of mycobacterium tuberculosis at a con centration of 0.2 mg./ cc. Whenused as bacteriostats, the present compounds are advantageously incorporated into organic solvents, say ethanol orisopropanoLor they may also be admixed with soaps or synthetic detergents. As fungicides, the present compounds are highly ,e'iiicient for preventing and retarding fungus growth'on textiles, for, leather, woods, etc. a For either fungicidal or insecticidal use "the 1, l,1-trichloro-2,2-bis[ carboalkoxyamino aryl] ethanes are generally applied in the form of sp iay$ r aerosols. Sprays may be prepared by dissolving the presently provided compounds in the usual organic solvents, e.g., acetone, hexane, benzene, carbon tetrachloride, kerosene, etc.; but it isprefer redto prepare the efliciency. The emulsions are readily made "by adding to one of the present compounds anemulsifying agent, if desired, first dissolving or suspending said compound in an organic solvent irnrnisciblewith water, i.e., an oil, before the addition of the emulsifying agent, and then mixing With water to-form an emulsion. Because of the very high biological efiiciency of the present reaction products, they need be present in the emulsion in only very small concentrations, for example, in concentrations of 100 to 10,000 parts per million by weight of the total emulsion. Emulsifying agents which may be employed are those customarily used in the art for the preparation of oil-in-water emulsions, e.g., long-chained polyalkylene glycols, long-chained alkyl sulfosuccinates, etc.

The present compounds may also be dissolved in liquefied gases uch as the fluorochloroethanes or methyl chloride and applied from aerosol bombs containing the solution.

Instead of employing liquids as carriers and diluents, pesticidal dusts comprising the present compounds may be prepared by grinding or milling the reaction products prepared in accordance with this invention with a pulverulent carrier. Kaolin,- hentonite, chalk, talc, etc. can be used a carriers. if desired, be used as additives, for example, in a composition comprising eighty partsof inert carrier, ten parts of active ingredient (the reactionproduct of the invention) and ten parts of adhesive or wetting agent additive.

' Such a Wettable powder may be further diluted with inert carrier to produce emulsions containing the powder in a concentration of from 0:1 to one, percent.

The present compoundsor compositions containing the same may usefully be applied directly to insects or fungi or they may be'applied'to the fruit or foliage of plants or other potential hosts in advance of the anticipated in- Wetting and adhesiyeag'ents may,.

festation. The term insect is herein used to include mites and allied classes of arthropods such as spiders, centipedes, etc., as well as true Hexapoda, i.e., six-legged invertebrates.

While the invention has been described with particular reference to various preferred embodiments thereof, it will be appreciated that numerous modifications and variations are possible Without departure from the invention and the invention is not to be limited to any specific embodiment thereof except as defined in the appended claims.

This application is a continuation-in-part of my application Serial No. 700,960, filed December 6, 1957, and now abandoned.

What I claim is:

1. An ester having the formula Cl CCH(ArNHCOOAlk) 2 wherein Ar is selected from the class consisting of phenyl, alkyl-substituted phenyl having from 7 to 12 carbon atoms, biphenylyl, naphthyl and alkyl-substituted naphthyl having a total of from 11 to 12 carbon atoms, and is attached to the remainder of the molecule of which it forms a part through a ring carbon atom thereof, and Alk denotes alkyl of from 1 to 5 carbon atoms.

2. A 1,1,1-trichloro-2,2-bis carboalkoxyamino) phenyl] ethane having from 1 to 5 carbon atoms in the alkoxy.

3. 1,1,1-trichloro-2,2-bis [4-(carbomethoxyamino)phenyl] ethane.

4. 1,1,1 trichloro 2,2-bis[(carboethoxyamino)-2- naphthyflethane.

References Cited in the file of this patent UNITED STATES PATENTS Muller Sept. 7, 1943 Caldwell July 30, 1957 OTHER REFERENCES Berlin et al.: Yasue et al.: 

1. AN ESTER HAVING THE FORMULA 